US5120882A - Nitrated metalloporphyrins as catalysts for alkane oxidation - Google Patents

Nitrated metalloporphyrins as catalysts for alkane oxidation Download PDF

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US5120882A
US5120882A US07/758,147 US75814791A US5120882A US 5120882 A US5120882 A US 5120882A US 75814791 A US75814791 A US 75814791A US 5120882 A US5120882 A US 5120882A
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process according
replaced
porphyrin ring
nitrated
metalloporphyrin
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US07/758,147
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Paul E. Ellis, Jr.
James E. Lyons
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Sunoco Inc R&M
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Sun Refining and Marketing Co
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Assigned to SUN REFINING AND MARKETING COMPANY A CORP. OF PENNSYLVANIA reassignment SUN REFINING AND MARKETING COMPANY A CORP. OF PENNSYLVANIA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ELLIS, PAUL E., JR., LYONS, JAMES E.
Priority to US07/892,106 priority patent/US5280115A/en
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Priority to NO923478A priority patent/NO923478D0/en
Priority to DE69209944T priority patent/DE69209944T2/en
Priority to CA002077983A priority patent/CA2077983A1/en
Priority to EP92308246A priority patent/EP0532326B1/en
Priority to JP4267792A priority patent/JPH05262684A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds

Definitions

  • This invention relates to oxidation of alkanes using metalloporphyrins as catalysts, and more particularly to such processes in which nitro groups have been substituted for hydrogen in the porphyrin ligand.
  • nitrated metalloporphyrins and nitrated/halogenated metalloporphyrins have utility a catalysts for the oxidation with oxygen-containing gas of alkanes such as methane, ethane, propane, butanes and the like.
  • the process of the invention comprises contacting alkane with oxygen-containing gas in the presence of a metalloporphyrin in which 12.5 to 100 percent of the hydrogen atoms in the porphyrin ring have been replaced with nitro groups.
  • the metal in the catalyst is selected from the group consisting of iron, chromium, manganese, ruthenium, cobalt or copper.
  • Other metals known for making metalloporphyrins may be used, but in general such other metalloporphyrins are less active than metalloporphyrins containing the preferred metals above.
  • the metalloporphyrin is substituted both with nitro groups and with halogen atoms.
  • a porphyrin substituted with 20 fluorine atoms and 8 nitro groups about 28 percent of the hydrogen atoms have been replaced with nitro groups and about 72 percent of the hydrogen atoms have been replaced with halogen atoms.
  • 1 to 8 of the pyrrolic hydrogens in the porphyrin ring have been replaced with nitro groups.
  • remaining hydrogens in the porphyrin ring have been replaced with halogen.
  • Specific catalysts useful according to the invention include nitrated meso-perfluorinatedalkylporphyrin, nitrated iron tetrakispentafluorylphenylporphyrin and metallomesotetranitroporphine.
  • the catalysts used in the invention are particularly effective in the oxidation of alkanes and alkenes, including cycloalkanes and cycloalkenes, substituted alkanes and alkenes and the like.
  • the starting materials include straight and branched-chain compounds having from about 1 to 2 carbon atoms, preferably 1 to 10 carbon atoms, such as methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methylheptane 3-methylheptane, the corresponding alkene forms, and the like., as well as cycloalkanes and cycloalkenes having from about 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane,
  • the oxidation which may be carried out in a generally known manner, is desirably conducted in the liquid phase, although this is not critical, using such organic solvents as benzene, acetic acid, acetonitrile, methyl acetate, or like solvents which are inert to the conditions of the reactions, or in a neat solution of the hydrocarbon if it is liquid, and under pressures ranging from about 15 to 1500 psig, preferably 30 to 750 psig, at temperature of from about 25 to 250o C., more preferably 70 to 180o C
  • the hydrocarbon to be oxidized is a solid, liquid or gas, it is dissolved in or bubbled through the solvent, together with air or oxygen, in the presence of the catalyst used according to the invention, for periods of time sufficient to yield the desired oxidation product, generally from about 0.5 to 100 hours, and more preferably from 1 to 10 hours.
  • solvent while not critical, can have an effect on the rates and selectivities obtained and should be carefully selected in order to optimize the desired results. For example, it has been found that solvents such as acetonitrile and acetic acid are often very effective for the oxidation of alkanes to form oxygen-containing compounds, whereas reactions carried out in solvents such as methyl acetate or benzene may occur more slowly. Thus, by routine experimentation, the optimum solvent for the particular process can be readily determined.
  • the ratios of the various reactants may vary widely, and are not critical.
  • the amount of catalyst employed can range from about 10 -6 to 10 -3 moles per mole of hydrocarbon such as alkane, and more preferably from about 10 -5 to 10 -4 mole of catalyst per mole of hydrocarbon, although other amounts are not precluded; while the amount of oxygen relative to the hydrocarbon starting material may also vary widely, generally 10 -2 to 10 2 moles of oxygen per mole of hydrocarbon. Care should be taken since some of the ratios fall within explosive limits. As a group, the catalysts are almost always soluble unless used in large excess. Thus, as a rule, the reactions are generally carried out homogeneously.
  • the catalysts used in the process of the invention may be made by any suitable method, of which the following are examples.
  • Iron tetrakispentafluorophenylporphine chloride is reacted with nitrogen dioxide (1-8) equivalents in methylene chloride or benzene leading to varying amounts of nitration at the beta positions on the ring according to the severity of the reaction conditions. Beta-positions left unnitrated are subsequently halogenated using normal chlorination, bromination or fluorination techniques.
  • the general structure for the products is: ##STR1## where M is Fe, Cr, Mn, Ru, Co or Cu, X is nitro, Y is nitro or Cl or Br or F and Z is H or Cl or Br or F.
  • Zn(porphine) is reacted with nitrogen dioxide in methylene chloride to produce Zn(mesotetranitroporphine).
  • the zinc is removed by acid treatment and Fe or other transition metal, M, is inserted by the usual method of ferrous chloride or MCl 2 in dimethylformamide.
  • the beta or pyrrolic hydrogens can be further nitrated or halogenated as desired.
  • the general formula is: ##STR2## where M is Fe, Cr, Mn, Ru, Cu or Co, X is nitro, and Y is nitro, Cl, F, Br or any combination thereof.
  • the catalyst prepared as described in Example 1 is used as a catalyst for the oxidation of isobutane to t-butyl alcohol in the following manner.
  • Isobutane (6-7 grams) is dissolved in 25 ml of benzene containing the catalyst, and air is added to a pressure of 100 psi.
  • Oxidation is carried out at a temperature of 60° C. for six hours.
  • Gaseous and liquid products are analyzed by gas chromatography and mass spectrometry.
  • Catalyst activity is expressed as "catalyst turnovers", i.e., moles of oxygen consumed/mole of catalyst.
  • Selectivity is the moles of TBA per mole of liquid product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Description

BACKGROUND OF THE INVENTION
This invention relates to oxidation of alkanes using metalloporphyrins as catalysts, and more particularly to such processes in which nitro groups have been substituted for hydrogen in the porphyrin ligand.
The use of metalloporphyrins as catalysts for the oxidation of hydrocarbons with air in the liquid phase has been shown in our U.S. Pat. Nos. 4,895,680 and 4,895,682 with the further finding that halogenation of the porphyrin ring led to even more active and stable catalysts (our U.S. Pat. Nos. 4,900,871 and 4,895,682 and pending application Ser. No. 568,118 filed Aug. 16, 1990). Since these discoveries we have been able to correlate increased electron withdrawal from halogenation of the porphyrin ring to increased catalytic air oxidation activity. J. E. Lyons and P. E. Ellis, Jr., Catalvsis Letters 8, 45 (1991).
It is also known that other functional groups besides halogens can lead to electron withdrawal in porphyrins. For example, L. C. Gong and D. Dolphin in Can. J. Chem., 63, 401 (1985) found that successive nitration at the meso positions of Zn(octaethylporphine) eventually giving Zn(mesotetranitrooctaethylporphine) led to more easily reduced porphyrins, evidence for electron withdrawal from the ring. Other workers such as Catalano, et.al. in J. Chem. Soc., 1535 (1984) have been able to nitrate the beta or pyrrolic positions in various metal tetraphenylporphyrins.
DESCRIPTION OF THE INVENTION
We have now found that nitrated metalloporphyrins and nitrated/halogenated metalloporphyrins have utility a catalysts for the oxidation with oxygen-containing gas of alkanes such as methane, ethane, propane, butanes and the like.
The process of the invention comprises contacting alkane with oxygen-containing gas in the presence of a metalloporphyrin in which 12.5 to 100 percent of the hydrogen atoms in the porphyrin ring have been replaced with nitro groups.
Preferably, the metal in the catalyst is selected from the group consisting of iron, chromium, manganese, ruthenium, cobalt or copper. Other metals known for making metalloporphyrins may be used, but in general such other metalloporphyrins are less active than metalloporphyrins containing the preferred metals above.
In one embodiment of the invention, the metalloporphyrin is substituted both with nitro groups and with halogen atoms. In such cases, preferably, 4 to 28 percent of the hydrogen atoms in the porphyrin ring have been replaced with nitro groups and 0 to 72 percent of the hydrogen atoms in the porphyrin ring have been replaced with halogen atoms. For example, in a porphyrin substituted with 20 fluorine atoms and 8 nitro groups, about 28 percent of the hydrogen atoms have been replaced with nitro groups and about 72 percent of the hydrogen atoms have been replaced with halogen atoms.
In one embodiment, 1 to 8 of the pyrrolic hydrogens in the porphyrin ring have been replaced with nitro groups. In a further embodiment, remaining hydrogens in the porphyrin ring have been replaced with halogen.
Preferably all of the hydrogen atoms have been replaced either with nitro groups or halogen atoms, but this is not essential.
Specific catalysts useful according to the invention include nitrated meso-perfluorinatedalkylporphyrin, nitrated iron tetrakispentafluorylphenylporphyrin and metallomesotetranitroporphine.
The catalysts used in the invention are particularly effective in the oxidation of alkanes and alkenes, including cycloalkanes and cycloalkenes, substituted alkanes and alkenes and the like. The starting materials include straight and branched-chain compounds having from about 1 to 2 carbon atoms, preferably 1 to 10 carbon atoms, such as methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methylheptane 3-methylheptane, the corresponding alkene forms, and the like., as well as cycloalkanes and cycloalkenes having from about 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, the corresponding alkene forms, and the like.
The oxidation, which may be carried out in a generally known manner, is desirably conducted in the liquid phase, although this is not critical, using such organic solvents as benzene, acetic acid, acetonitrile, methyl acetate, or like solvents which are inert to the conditions of the reactions, or in a neat solution of the hydrocarbon if it is liquid, and under pressures ranging from about 15 to 1500 psig, preferably 30 to 750 psig, at temperature of from about 25 to 250o C., more preferably 70 to 180o C Depending upon whether the hydrocarbon to be oxidized is a solid, liquid or gas, it is dissolved in or bubbled through the solvent, together with air or oxygen, in the presence of the catalyst used according to the invention, for periods of time sufficient to yield the desired oxidation product, generally from about 0.5 to 100 hours, and more preferably from 1 to 10 hours.
The choice of solvent, while not critical, can have an effect on the rates and selectivities obtained and should be carefully selected in order to optimize the desired results. For example, it has been found that solvents such as acetonitrile and acetic acid are often very effective for the oxidation of alkanes to form oxygen-containing compounds, whereas reactions carried out in solvents such as methyl acetate or benzene may occur more slowly. Thus, by routine experimentation, the optimum solvent for the particular process can be readily determined.
The ratios of the various reactants may vary widely, and are not critical. For example, the amount of catalyst employed can range from about 10-6 to 10-3 moles per mole of hydrocarbon such as alkane, and more preferably from about 10-5 to 10-4 mole of catalyst per mole of hydrocarbon, although other amounts are not precluded; while the amount of oxygen relative to the hydrocarbon starting material may also vary widely, generally 10-2 to 102 moles of oxygen per mole of hydrocarbon. Care should be taken since some of the ratios fall within explosive limits. As a group, the catalysts are almost always soluble unless used in large excess. Thus, as a rule, the reactions are generally carried out homogeneously.
The catalysts used in the process of the invention may be made by any suitable method, of which the following are examples.
EXAMPLE 1
Iron tetrakispentafluorophenylporphine chloride is reacted with nitrogen dioxide (1-8) equivalents in methylene chloride or benzene leading to varying amounts of nitration at the beta positions on the ring according to the severity of the reaction conditions. Beta-positions left unnitrated are subsequently halogenated using normal chlorination, bromination or fluorination techniques. The general structure for the products is: ##STR1## where M is Fe, Cr, Mn, Ru, Co or Cu, X is nitro, Y is nitro or Cl or Br or F and Z is H or Cl or Br or F.
EXAMPLE 2
Zn(porphine) is reacted with nitrogen dioxide in methylene chloride to produce Zn(mesotetranitroporphine). The zinc is removed by acid treatment and Fe or other transition metal, M, is inserted by the usual method of ferrous chloride or MCl2 in dimethylformamide. The beta or pyrrolic hydrogens can be further nitrated or halogenated as desired. The general formula is: ##STR2## where M is Fe, Cr, Mn, Ru, Cu or Co, X is nitro, and Y is nitro, Cl, F, Br or any combination thereof.
EXAMPLE 3
Meso-perfluorinated alkyl porphyrins, made as disclosed in our copending application Serial No. 568,118 filed Aug. 16, 1990, the disclosure of which is herein incorporated by reference, can be nitrated in the beta or pyrrolic positions using nitrogen dioxide in methylene dichloride or nitric acid/sulfuric acid nitrating solutions. The general structure is: ##STR3## where M is Fe, Cr, Mn, Ru, Cu or Co, X is 0-6, and Y is nitro and Z is NO2 or Cl or Br or F.
The invention will be further disclosed with reference to the following examples.
EXAMPLE 4
The catalyst prepared as described in Example 1 is used as a catalyst for the oxidation of isobutane to t-butyl alcohol in the following manner. Isobutane (6-7 grams) is dissolved in 25 ml of benzene containing the catalyst, and air is added to a pressure of 100 psi. Oxidation is carried out at a temperature of 60° C. for six hours. Gaseous and liquid products are analyzed by gas chromatography and mass spectrometry. Catalyst activity is expressed as "catalyst turnovers", i.e., moles of oxygen consumed/mole of catalyst. Selectivity is the moles of TBA per mole of liquid product. Higher numbers of catalyst turnovers and/or greater selectivity are obtained with the catalyst of the invention as compared with otherwise similar catalyst which has not been substituted with nitro groups. Similar results are obtained when the catalysts of Examples 2 and 3 above are used as alkane oxidation catalysts.

Claims (8)

The invention claimed is:
1. Process for oxidation of alkanes which comprises contacting alkane with oxygen-containing gas in the presence of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with at least one nitro group.
2. Process according to claim 1 in which the metalloporphyrin contains iron, chromium, manganese, ruthenium, cobalt or copper.
3. Process according to claim 1 in which 1 to 8 of the pyrrolic hydrogen atoms in the porphyrin ring have bee replaced with nitro groups.
4. Process according to claim 3 in which remaining hydrogen atom in the porphyrin ring have been substituted with halogen atoms.
5. Process according to claim 4 in which 4 to 8 hydrogen atoms in the porphyrin ring have been replaced with nitro groups and in which 8 to 20 hydrogen atoms in the porphyrin ring have been replaced with halogen.
6. Process according to claim 1 in which the metalloporphyrin is a nitrated, mesoperfluorinated alkylporphyrin.
7. Process according to claim 1 in which the metalloporphyrin is a nitrated iron tetrakispentafluorophenylporphine.
8. Process according to claim 1 wherein the metalloporphyrin is a metallomesotetranitroporphine.
US07/758,147 1991-09-12 1991-09-12 Nitrated metalloporphyrins as catalysts for alkane oxidation Expired - Fee Related US5120882A (en)

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US07/758,147 US5120882A (en) 1991-09-12 1991-09-12 Nitrated metalloporphyrins as catalysts for alkane oxidation
US07/892,106 US5280115A (en) 1991-09-12 1992-06-02 Nitrated metalloporphyrins as catalysts for alkane oxidation
NO923478A NO923478D0 (en) 1991-09-12 1992-09-07 NITRATED METAL FORPHYRINE CATALYSTS
DE69209944T DE69209944T2 (en) 1991-09-12 1992-09-10 Nitrated metalloporphyrins as catalysts in the oxidation of alkanes
CA002077983A CA2077983A1 (en) 1991-09-12 1992-09-10 Nitrated metalloporphyrins as catalysts for alkane oxidation
EP92308246A EP0532326B1 (en) 1991-09-12 1992-09-10 Nitrated metalloporphyrins as catalysts for alkane oxidation
JP4267792A JPH05262684A (en) 1991-09-12 1992-09-11 Nitrated metalloporphyrins as catalyst for alkane oxidation

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Cited By (20)

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EP0296712A2 (en) 1987-06-26 1988-12-28 SUN COMPANY, INC. (R&M) Hydrocarbon oxidations catalyzed by iron coordination complexes containing a halogenated ligand
US5241062A (en) * 1993-01-19 1993-08-31 Sun Company, Inc. (R&M) Synthetic route to meso-tetra hydrocarbyl or substituted hydrocarbyl porphyrins and derivatives
US5280115A (en) * 1991-09-12 1994-01-18 Sun Company, Inc. (R&M) Nitrated metalloporphyrins as catalysts for alkane oxidation
EP0665056A3 (en) * 1993-12-29 1995-08-09 Sun Co Inc R & M
US5464741A (en) * 1993-10-08 1995-11-07 Henwell, Inc. Palladium (II) octaethylporphine alpha-isothiocyanate as a phosphorescent label for immunoassays
US5480986A (en) * 1993-07-30 1996-01-02 Sun Company, Inc. (R&M) Metal complexes of substituted Gable porphyrins as oxidation catalysts
EP0665230A3 (en) * 1993-12-29 1996-01-17 Sun Co Inc R & M Halocaryl-substituted porphyrins and their synthesis from mes-halocaryl-dipyrromethanes and aldehydes.
US5489716A (en) * 1987-01-02 1996-02-06 Sun Company, Inc. (R&M) Reactions catalyzed by haloporphyrins
US5493017A (en) * 1992-08-14 1996-02-20 The Trustees Of The University Of Pennsylvania Ring-metalated porphyrins
US5502211A (en) * 1993-10-26 1996-03-26 Sun Company, Inc. (R&M) Substituted dipyrromethanes and their preparation
US5599948A (en) * 1995-11-27 1997-02-04 Sun Company, Inc. Substituted dipyrromethanes and their preparation
US5599924A (en) * 1992-08-14 1997-02-04 Trustees Of The University Of Pennsylvania Electron-deficient porphyrins and processes and intermediates for preparing same
US5608054A (en) * 1993-12-29 1997-03-04 Sun Company, Inc. (R&M) Porphyrins and metal complexes thereof having haloalkyl side chains
EP0781744A2 (en) 1995-12-29 1997-07-02 SUN COMPANY, INC. (R&M) Catalytic oxidation of light alkanes in presence of a base
US5663328A (en) * 1987-01-02 1997-09-02 Sun Company, Inc. (R&M) Haloporphyrins and their preparation and use as catalysts
US5756723A (en) * 1992-08-14 1998-05-26 The Trustees Of The University Of Pennsylvania Metal-mediated cross-coupling with ring-metalated porphyrins
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
US6002026A (en) * 1996-07-26 1999-12-14 The Trustees Of Princeton University Catalytic oxygenation of hydrocarbons by metalloporphyrin and metallosalen complexes
US6124452A (en) * 1997-12-19 2000-09-26 University Of Nebraska-Lincoln Octafluoro-meso-tetraarylporphyrins and methods for making these compounds
CN104914094A (en) * 2010-02-04 2015-09-16 光谱系统公司 Gas activated changes to ligth absorption and emission characteristics for security articles

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Cited By (28)

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US5489716A (en) * 1987-01-02 1996-02-06 Sun Company, Inc. (R&M) Reactions catalyzed by haloporphyrins
US5990363A (en) * 1987-01-02 1999-11-23 Sun Company, Inc. Method for oxidizing alkanes using novel porphyrins synthesized from dipyrromethanes and aldehydes
US5723677A (en) * 1987-01-02 1998-03-03 Sun Company, Inc. (R&M) Method for hydroperoxide decomposition using novel porphyrins synthesized from dipyrromethanes and aldehydes
US5663328A (en) * 1987-01-02 1997-09-02 Sun Company, Inc. (R&M) Haloporphyrins and their preparation and use as catalysts
US5571908A (en) * 1987-01-02 1996-11-05 Sun Company, Inc. (R&M) Porphyrins
EP0296712A2 (en) 1987-06-26 1988-12-28 SUN COMPANY, INC. (R&M) Hydrocarbon oxidations catalyzed by iron coordination complexes containing a halogenated ligand
US5280115A (en) * 1991-09-12 1994-01-18 Sun Company, Inc. (R&M) Nitrated metalloporphyrins as catalysts for alkane oxidation
US5817830A (en) * 1992-08-14 1998-10-06 Trustees Of The University Of Pennsylvania Pyrrolic compounds
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